JP2009007372A - N-sulphonylaminoacetonitrile having pesticidal properties - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a parasiticide and a parasiticidal method. <P>SOLUTION: The invention relates to compounds of general formula (I) and enantiomers thereof. The active compounds have advantageous pesticidal properties. They are suitable, in particular, for the control of parasites in warm-blooded animals. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention has the formula:

［式中、Ｒ_１は、それぞれの場合に、置換されていないか又はＲ_７によって単若しくは多置換されているアリール又はヘテロアリール（ここで、置換基は、それぞれの場合に、それらの数が１よりも大きい場合に、同一か又は異なっていてよい）であり、
Ｒ_２は、Ｃ_１〜Ｃ_６アルキル、ハロ−Ｃ_１〜Ｃ_６アルキル、Ｃ_３〜Ｃ_８シクロアルキル、ハロ−Ｃ_３〜Ｃ_８シクロアルキル、ＮＨＲ_８、それぞれの場合に、置換されていないか又はＲ_７によって単若しくは多置換されているアリール若しくはヘテロアリール（ここで、置換基は、それぞれの場合に、それらの数が１よりも大きい場合に、同一か又は異なっていてよい）であり又はそれぞれの場合にＮを介して結合している、ピロリジニル、ピペリジニル、イミダゾリジニル、ピペラジニル、ピラゾリジニル、モルホリニル、インドリニル若しくはイソインドリニルであり、
Ｒ_３は、水素、Ｃ_１〜Ｃ_６アルキル、ハロ−Ｃ_１〜Ｃ_６アルキル、Ｃ_１〜Ｃ_６アルコキシ−Ｃ_１〜Ｃ_６アルキル、ベンジル、Ｃ_１〜Ｃ_６アルキルヘテロアリール、Ｃ_１〜Ｃ_６アルコキシカルボニル又はＣ_１〜Ｃ_６アルキルカルボニルであり、
Ｒ_４、Ｒ_５及びＲ_６は、互いに独立に、水素、ハロゲン、Ｃ_１〜Ｃ_６アルキル、ハロ−Ｃ_１〜Ｃ_６アルキル、Ｃ_１〜Ｃ_６アルコキシ、ハロ−Ｃ_１〜Ｃ_６アルコキシ、Ｃ_１〜Ｃ_６アルキルチオ、ハロ−Ｃ_１〜Ｃ_６アルキルチオ、Ｃ_２〜Ｃ_６アルケニル、Ｃ_２〜Ｃ_６アルキニル、置換されていない若しくは置換されたＣ_３〜Ｃ_８シクロアルキル（ここで、置換基は、ハロゲン及びＣ_１〜Ｃ_６アルキルからなる群から選択される）又は置換されていない若しくは置換されたフェニル（ここで、置換基は、ハロゲン、Ｃ_１〜Ｃ_６アルキル及びフェニルからなる群から選択される）であり、又は
Ｒ_４及びＲ_５は、それらが結合している炭素原子と一緒に、１から２個の、窒素、酸素及び硫黄からなる群から選択されたヘテロ原子を有する、５から７員の飽和若しくは部分的不飽和複素環式環であり、
Ｒ_７は、ハロゲン、Ｃ_１〜Ｃ_６アルキル、ハロ−Ｃ_１〜Ｃ_６アルキル、Ｃ_１〜Ｃ_６アルコキシ、ハロ−Ｃ_１〜Ｃ_６アルコキシ、Ｃ_１〜Ｃ_６アルキルチオ、ハロ−Ｃ_１〜Ｃ_６アルキルチオ、Ｃ_２〜Ｃ_６アルケニル、Ｃ_２〜Ｃ_６アルキニル、それぞれの場合に、置換されていないか又は単若しくは多置換されているアリール、フェニルアセチレニル又はヘテロアリール（ここで、置換基は、それぞれの場合に、ハロゲン、ニトロ、シアノ、Ｃ_１〜Ｃ_６アルキル、ハロ−Ｃ_１〜Ｃ_６アルキル、Ｃ_１〜Ｃ_６アルコキシ、ハロ−Ｃ_１〜Ｃ_６アルコキシからなる群から選択され、およびそれぞれの場合に、それらの数が１よりも大きい場合に、同一か又は異なっていてよい）であり、
Ｒ_８は、置換されていないか又は一から五置換されているアリール（ここで、置換基は、ハロゲン、ニトロ、シアノ、Ｃ_１〜Ｃ_６アルキル、ハロ−Ｃ_１〜Ｃ_６アルキル、Ｃ_１〜Ｃ_６アルコキシ及びハロ−Ｃ_１〜Ｃ_６アルコキシからなる群から選択され、および、それらの数が１よりも大きい場合に、同一か又は異なっていてよい）であり、
Ｘは、Ｏ、Ｓ、Ｓ（Ｏ）又はＳ（Ｏ）_２であり、
ｎは０又は１である］
の新規なスルホニルアミノアセトニトリル化合物並びに適切な場合に、それぞれの場合に遊離形又は塩形での、Ｅ／Ｚ異性体、Ｅ／Ｚ異性体混合物及び／又は互変異性体；
これらの化合物、それらの異性体及び互変異性体の製造方法及び使用；式（Ｉ）の化合物の製造のための出発化合物；活性化合物が式（Ｉ）の化合物及びそれらの互変異性体から選択される病虫害防除剤並びにこれらの組成物を使用する、植物有害昆虫、並びに、温血農業用及び家庭内動物内及び上の、ダニ目並びに内部寄生虫及び外部寄生虫の代表、特に蠕虫の駆除方法に関する。

Wherein R ₁ is in each case aryl or heteroaryl which is unsubstituted or mono- or polysubstituted by R ₇ (wherein the substituents are in each case the number of which They may be the same or different if they are greater than 1),
R ₂ is C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkyl, C ₃ -C ₈ cycloalkyl, halo-C ₃ -C ₈ cycloalkyl, NHR ₈ , in each case unsubstituted Or aryl or heteroaryl which is mono- or polysubstituted by R ₇ (wherein the substituents may in each case be the same or different when their number is greater than 1) Or pyrrolidinyl, piperidinyl, imidazolidinyl, piperazinyl, pyrazolidinyl, morpholinyl, indolinyl or isoindolinyl linked in each case via N;
R ₃ is hydrogen, C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl, benzyl, C ₁ -C ₆ alkyl heteroaryl, C _1- a C ₆ alkoxycarbonyl or _C 1 -C ₆ alkylcarbonyl,
R ₄ , R ₅ and R ₆ are independently of each other hydrogen, halogen, C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halo-C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, halo _-C 1 -C _{6 alkylthio,} C 2 -C _{6 alkenyl,} C 2 -C ₆ alkynyl, unsubstituted or substituted by a _C 3 -C ₈ cycloalkyl (wherein the substituted group selected from the group consisting of halogen and C ₁ -C selected from the group consisting of ₆ alkyl) or unsubstituted or substituted phenyl (wherein the substituents are made from halogen, C ₁ -C ₆ alkyl and phenyl Or R ₄ and R ₅ are selected from the group consisting of 1 to 2 nitrogen, oxygen and sulfur, together with the carbon atom to which they are attached. A 5- to 7-membered saturated or partially unsaturated heterocyclic ring having atoms;
R ₇ is halogen, C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halo-C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, halo-C _1- C ₆ alkylthio, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, in each case unsubstituted, mono- or polysubstituted aryl, phenylacetylenyl or heteroaryl (wherein selection group is in each case halogen, nitro, _cyano, C 1 -C ₆ alkyl, halo _-C 1 -C _{6 alkyl,} C 1 -C ₆ alkoxy, from the group consisting of halo _-C 1 -C ₆ alkoxy And in each case may be the same or different if their number is greater than 1),
R ₈ is unsubstituted or substituted 1 to 5 substituted aryl (wherein the substituents are halogen, nitro, cyano, C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy and halo-C ₁ -C ₆ alkoxy and may be the same or different when their number is greater than 1)
X is, O, S, an S (O) or S _{(O) 2,}
n is 0 or 1]
The novel sulfonylaminoacetonitrile compounds and, where appropriate, in each case in the free or salt form, E / Z isomers, E / Z isomer mixtures and / or tautomers;
Preparation and use of these compounds, their isomers and tautomers; starting compounds for the preparation of compounds of formula (I); active compounds from compounds of formula (I) and their tautomers Pest control agents selected and representatives of ticks and endoparasites and ectoparasites, especially helminths in and on warm-blooded agricultural and domestic animals, using these pest control agents and compositions thereof It relates to the removal method.

  Substituted aminoacetonitrile compounds having pest control action are described in the literature. However, the active compounds actually disclosed therein do not always meet the requirements for efficacy and zone of action. Accordingly, there is a need for active compounds with improved pest control properties.

  It has been found that the compounds of the formula (I) according to the invention have significant pest control properties, in particular against agricultural and domestic animals and plants and on endoparasites and ectoparasites. It was.

  Some of the compounds of formula (I) may be in the form of tautomers. Accordingly, a compound of formula (I) is understood herein to include the corresponding tautomers where appropriate, even though tautomers are not specifically described in each case. It should be.

Certain of the compounds of formula (I) and, where appropriate, their tautomers can form salts, eg, acid addition salts. These acid addition salts are (for example, mineral acids such as sulfuric acid, phosphoric acid or a hydrohalic acid) strong inorganic acids, such as, (as that is not or substituted substituted, C ₁ -C eg halo-substituted ₄ Alkanecarboxylic acids such as acetic acid, saturated or unsaturated dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, fumaric acid and phthalic acid, hydroxycarboxylic acids such as ascorbic acid, lactic acid, malic acid, tartaric acid and citric acid or benzoic acid Strong organic carboxylic acids (such as acids) or (unsubstituted or substituted, eg halo substituted, C ₁ -C ₄ alkane- or aryl sulfonic acids, eg methane- or p-toluene sulfonic acids ) Formed with organic sulfonic acid. Furthermore, compounds of formula (I) having at least one acid group can form salts with bases. Salts with suitable bases include metal salts (such as alkali and alkaline earth metal salts such as sodium, potassium and magnesium salts) and ammonia or morpholine, piperidine, pyrrolidine, mono-, di- or tris. Lower alkyl amines such as ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine or mono-, di- or trihydroxy lower alkyl amines such as mono-, di- or triethanolamine) It is salt. In addition, corresponding internal salts can optionally be formed. The free form is first preferred. Of the salts of the compound of formula (I), pesticidally advantageous salts are preferred. The free compounds of formula (I) and their salts are to be understood here as including both the corresponding salts and free compounds of the compounds of formula (I), respectively, where appropriate. is there. The same is correspondingly true for tautomers of the compounds of formula (I) and their salts.

  The general terms used herein have the following meanings unless otherwise defined.

  Aryl is phenyl or naphthyl.

  Heteroaryl is pyridyl, pyrimidyl, s-triazinyl, 1,2,4-triazinyl, thienyl, furanyl, pyryl, pyrazolyl, imidazolyl, thiazolyl, triazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, benzothienyl, benzofuranyl, benzothiazolyl, Indolyl or indazolyl, preferably pyridyl, pyrimidyl, s-triazinyl or 1,2,4-triazinyl, especially pyridyl or pyrimidyl.

  Alkyl is the number of carbon atoms contained in the corresponding group or compound, in each case, as a group itself and as a structural element of other groups and compounds such as halo-alkyl, alkoxy and alkylthio. Straight chain alkyl, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl or branched alkyl, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or Isohexyl.

  Alkenyl is the number of carbon atoms and conjugated double bonds or lone double bonds contained in the corresponding group or compound, in each case in each case, as a group itself and as a structural element of other groups and compounds. Linear alkenyl such as allyl, 2-butenyl, 3-pentenyl, 1-hexenyl, 1-heptenyl, 1,3-hexadienyl or 1,3-octadienyl or branched alkenyl such as isopropenyl , Isobutenyl, isoprenyl, tert-pentenyl, isohexenyl, isoheptenyl or isooctenyl.

  Alkynyl, as the group itself and as a structural element of other groups and compounds, in each case, in each case, the number of carbon atoms and conjugated double bonds or isolated double bonds contained in the corresponding group or compound Straight chain alkynyl, for example propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl, 3-hexen-1-ynyl or 1,5-heptadien-3-ynyl or branched Chain alkynyl, for example 3-methylbut-1-ynyl, 4-ethylpent-1-ynyl, 4-methylhex-2-ynyl or 2-methylhept-3-ynyl.

  Cycloalkyl takes into account, in each case, the number of carbon atoms contained in the corresponding group or compound as a group itself and as a structural element of other groups and compounds such as halocycloalkyl. And cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

  Halogen is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, especially fluorine or chlorine, as the group itself and as a structural element of other groups and compounds such as haloalkyl, haloalkoxy and haloalkylthio .

Halogen-substituted carbon-containing groups and compounds such as haloalkyl, haloalkoxy or haloalkylthio may be partially halogenated or perhalogenated and are identical when polysubstituted with respect to the halogen substituent Or different. Examples of haloalkyl as the group itself and other groups such as haloalkoxy or haloalkylthio and structural elements of compounds include methyl monosubstituted by fluorine, chlorine and / or bromine such as CHF ₂ or CF ₃ Fluorine, such as CH ₂ CF ₃ , CF ₂ CF ₃ , CF ₂ CCl ₃ , CF ₂ CHCl ₂ , CF ₂ CHF ₂ , CF ₂ CFCl ₂ , CF ₂ CHBr ₂ , CF ₂ CHClF, CH ₂ CHBrF or CClFCHClF , Fluorine and chlorine and / or bromine, such as ethyl substituted by 1 to 5 with chlorine and / or bromine; CH ₂ CHBrCH ₂ Br, CF ₂ CHFCF ₃ , CH ₂ CF ₂ CF ₃ or CH (CF ₃ ) ₂ is seven substituted from scratch by a propyl or _isopropyl; CF (CF 3) CHFCF Butyl or one of its isomers substituted with 1 to 9 fluorine, chlorine and / or bromine, such as ₃ or CH ₂ (CF ₂ ) ₂ CF ₃ ; CF (CF ₃ ) (CHF) ₂ CF ₃ or CH _{2 (CF 2)} such as 3 CF _3, fluorine, one chlorine and / or one to eleven-substituted pentyl or an isomer by bromination and _{(CH 2) 4 CHBrCH 2 Br} , CF 2 (CHF ) Hexyl substituted by fluorine, chlorine and / or bromine, such as ₄ CF ₃ , CH ₂ (CF ₂ ) ₄ CF ₃ or C (CF ₃ ) ₂ (CHF) ₂ CF ₃ , or isomers thereof It is a kind of body.

  The alkoxy group preferably has a chain length of 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and the isomers pentyloxy and hexyloxy, preferably methoxy and ethoxy. Haloalkoxy groups preferably have a chain length of 1 to 6 carbon atoms. Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2, 2-difluoroethoxy and 2,2,2-trichloroethoxy, preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

  The alkylthio group preferably has a chain length of 1 to 6 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio.

  Preferred embodiments within the scope of the present invention are as follows in view of the above conditions.

(1) aryls in which R ₁ is unsubstituted or substituted one to five by R ₇ (wherein the substituents are identical in each case when their number is greater than 1 or May be different), in particular aryl substituted one to three by R ₇ (wherein the substituents may be the same or different in each case when their number is greater than 1). A compound of formula (I) which is
(2) C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkyl, aryl or heteroaryl (wherein R ₂ is in each case unsubstituted or mono- to polysubstituted by R ₇ ( Here, the substituents may in each case be the same or different if their number is greater than 1), in particular unsubstituted or substituted 1 to 5 by R ₇ . C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkyl or aryl (wherein the substituents may be the same or different when their number is greater than 1), in particular, substituted An aryl that is not substituted or is mono- to tri-substituted by R ₇ , where the substituents may be the same or different when their number is greater than 1; Compound of ;
(3) Compounds of formula (I), wherein R ₃ is hydrogen or C ₁ -C ₆ alkyl, in particular hydrogen or C ₁ -C ₄ alkyl, in particular hydrogen;
(4) R ₄ , R ₅ and R ₆ are independently of each other hydrogen, C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halo-C ₁ -C ₆ alkoxy , _C 2 -C _{6 alkenyl,} C 2 -C _{6 alkynyl,} C 3 -C ₆ cycloalkyl, in particular, _hydrogen, C 1 -C ₄ alkyl, halo _-C 1 -C ₄ alkyl or _C 3 -C ₆ cycloalkyl A compound of formula (I), in particular hydrogen or C ₁ -C ₂ alkyl;
(5) _{R 7} is halogen, in each case, is or mono- or polysubstituted _{unsubstituted,} C 1 -C ₄ alkyl, halo _-C 1 -C _{4 alkyl,} C 1 -C ₄ alkoxy , Halo-C ₁ -C ₄ alkoxy, aryl or phenylacetylenyl (wherein the substituents are halogen, C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halo -C ₁ -C ₆ alkoxy, and in each case may be the same or different when their number is greater than 1), in particular halogen, C ₁ -C ₂ alkyl A compound of formula (I), which is halo-C ₁ -C ₂ alkyl, C ₁ -C ₂ alkoxy, halo-C ₁ -C ₂ alkoxy, especially halogen or halo-C ₁ -C ₂ alkyl object;
(6) R ₈ is unsubstituted or mono- to tri-substituted aryl (wherein the substituents are halogen, C ₁ -C ₄ alkyl, halo-C ₁ -C ₄ alkyl, C _1- Selected from the group consisting of C ₄ alkoxy and halo-C ₁ -C ₄ alkoxy and may be the same or different when their number is greater than 1), in particular from 1 to 3 substituted Aryl (wherein the substituent is selected from the group consisting of halogen, C ₁ -C ₂ alkyl, halo-C ₁ -C ₂ alkyl and halo-C ₁ -C ₂ alkoxy, and the number thereof is from 1 May also be the same or different, especially, mono- or di-substituted aryl, wherein the substituent is selected from the group consisting of halogen and halo-C ₁ -C ₂ alkyl; Oh And the compounds of formula (I) may be the same or different when their number is greater than 1);
(7) Compounds of formula (I), wherein X is O or S, especially O;
(8) the compound of formula (I), wherein n is 1;
(9) aryl in which R ₁ is unsubstituted or substituted one to five by R ₇ (wherein the substituents are the same in each case when their number is greater than 1 or different is not be), _{R 2} is, in each case, are single or multi-substituted by one or _{R 7} is _{unsubstituted,} C 1 -C ₆ alkyl, halo _-C 1 -C ₆ alkyl, Aryl or heteroaryl, wherein the substituents may be the same or different in each case when their number is greater than 1, and R ₃ is hydrogen or C ₁ -C ₆ C ₁ -C ₆ alkyl, halo-C ₁ , wherein R ₄ , R ₅ and R ₆ are, independently of one another, hydrogen, in each case unsubstituted or mono- or polysubstituted ~C ₆ alkyl, ₁ -C ₆ alkoxy, halo _-C 1 -C _{6 alkoxy,} C 2 -C _{6 alkenyl,} C 2 -C _{6 alkynyl,} C 3 -C ₆ cycloalkyl, _{R 7} is _halogen, C 1 -C ₄ Alkyl, halo-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halo-C ₁ -C ₄ alkoxy, aryl or phenylacetylenyl (wherein the substituent is halogen, C ₁ -C ₆ alkyl, Are selected from the group consisting of halo-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halo-C ₁ -C ₆ alkoxy, and in each case, when their number is greater than 1, or a different may have), R ₈ is aryl which is trisubstituted or from one unsubstituted (wherein the substituents are halogen, C ₁ -C ₄ alkyl, halo -C ₁ ~ ₄ alkyl _is selected from the group consisting of C 1 -C ₄ alkoxy and halo _-C 1 -C ₄ alkoxy, and, if their number is greater than 1, the same or may be different), X A compound of formula (I) wherein is O or S and n is 1;
(10) aryl in which R ₁ is mono- to tri-substituted by R ₇ (wherein the substituents may be the same or different in each case when their number is greater than 1) C ₁ -C ₆ alkyl, halo-C ₁ -C ₆ alkyl or aryl, wherein R ₂ is unsubstituted or substituted 1 to 5 by R ₇ , where the substituents are R ₃ is hydrogen or C ₁ -C ₄ alkyl, and R ₄ , R ₅ and R ₆ are independently of each other, may be the same or different when the number of Hydrogen, C ₁ -C ₄ alkyl, halo-C ₁ -C ₄ alkyl or C ₃ -C ₆ cycloalkyl, R ₇ is halogen, C ₁ -C ₂ alkyl, halo-C ₁ -C ₂ alkyl, C ₁ -C ₂ alkoxy or halo -C ₁ -C is ₂ alkoxy, _{R 8} is aryl (where that is trisubstituted from scratch, the substituents are _halogen, C 1 -C ₂ alkyl, halo _-C 1 -C ₂ alkyl and halo -C ₁ A group selected from the group consisting of ˜C ₂ alkoxy and may be the same or different when their number is greater than 1), X is O, and n is 1. Compounds of I);
(11) aryl in which R ₁ is mono- to tri-substituted by R ₇ (wherein the substituents may be the same or different in each case when their number is greater than 1) And R ₂ is unsubstituted or substituted one to three by R ₇ (wherein the substituents are the same in each case when their number is greater than 1). Or R ₃ is hydrogen, R ₄ , R ₅ and R ₆ are independently of each other hydrogen or C ₁ -C ₂ alkyl, and R ₇ is halogen or halo- C ₁ -C ₂ alkyl, wherein R ₈ is mono- or disubstituted aryl, wherein the substituent is selected from the group consisting of halogen and halo-C ₁ -C ₂ alkyl, and Same if the number is greater than 1 Or a different may have), X is O, and n is 1, compounds of formula (I).

  Particularly preferred compounds of formula (I) for the purposes of the present invention are those listed in Tables 1 and 2, with the compounds of formula (I) described in the synthesis examples being particularly preferred.

  Another subject of the invention is a process for the preparation of a compound of formula (I), in each case in free or salt form,

の化合物（この化合物は、公知であるか又は対応する公知の化合物と同様にして製造することができ、式中のＲ_１、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｘ及びｎは、式（Ｉ）について定義された通りである）を、式：

(This compound is known or can be prepared in the same manner as the corresponding known compound, in which R ₁ , R ₃ , R ₄ , R ₅ , R ₆ , X and n are Is as defined for formula (I):

の化合物（この化合物は、公知であるか又は対応する公知の化合物と同様にして製造することができ、式中のＲ_２は、式（Ｉ）について定義された通りであり、およびＱは離脱基である）と、適切な場合に塩基性触媒の存在下で、反応させること、ならびに、それぞれの場合に、所望により、この方法に従って又は他の方法で得ることができるそれぞれの場合に遊離形又は塩形での式（Ｉ）の化合物を式（Ｉ）の他の化合物に転換し、この方法に従って得ることができる異性体の混合物を分離し、および所望の異性体を単離し及び／又はこの方法に従って得ることができる式（Ｉ）の遊離化合物を塩に転換するか又はこの方法に従って得ることができる式（Ｉ）の化合物の塩を式（Ｉ）の遊離化合物若しくは他の塩に転換すること、を特徴とする方法である。

(This compound is known or can be prepared analogously to the corresponding known compound, wherein R ₂ is as defined for formula (I) and Q is In each case in the presence of a basic catalyst, and in each case, if desired, can be obtained according to this method or otherwise in each case in the free form. Or converting a compound of formula (I) in salt form to another compound of formula (I), separating a mixture of isomers obtainable according to this process, and isolating the desired isomer and / or The free compound of formula (I) obtainable according to this method is converted into a salt or the salt of the compound of formula (I) obtainable according to this method is converted into a free compound of formula (I) or other salt To do, with features It is a method to do.

  What applies to the salts of the compounds of the formula (I) applies in the same way as described above to the salts for the starting materials described above and below.

  The reactants can be reacted with each other without adding a solvent or diluent, for example, in a molten state. However, it is usually advantageous to add inert solvents or diluents or mixtures thereof. Examples of such solvents or diluents that may be mentioned are aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromo Benzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethane or tetrachloroethane; ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or geo Sun; ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone; amides such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoramide; Nitriles such as acetonitrile or propionitrile as well as sulfoxides such as dimethyl sulfoxide.

  Preferred leaving groups are halogen, especially chlorine.

  Suitable bases to facilitate this reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkoxides, acetates, carbonates, dialkylamides or alkylsilylamides, alkylamines, Alkylene diamines, free or N-alkylated, unsaturated or saturated cycloalkylamines, basic heterocycles, ammonium hydroxides as well as carbocyclic amines. Examples that may be mentioned are sodium hydroxide, hydride, amide, methoxide, acetate, carbonate, potassium t-butoxide, hydroxide, carbonate, hydride, lithium diisopropylamide, potassium bis (trimethylsilyl). ) Amide, calcium hydride, triethylamine, diisopropylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N, N-dimethylamine, N, N-diethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, Quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,5-diazabicyclo [5.4.0] undec-5-ene (DBU).

  This reaction is advantageously carried out within a temperature range of about 0 ° C. to about + 150 ° C., preferably about 20 ° C. to about + 100 ° C.

  Another subject of the invention is a process for the preparation of compounds of formula (II), in each case in free or salt form, for example the formula:

の化合物（この化合物は、公知であるか又は対応する公知の化合物と同様にして製造することができ、式中のＲ_１、Ｒ_４、Ｒ_５、Ｒ_６、Ｘ及びｎは、式（Ｉ）について定義された通りである）を、無機又は有機シアン化物及び式Ｒ_３−ＮＨ_２の化合物（この化合物は、公知であるか又は対応する公知の化合物と同様にして製造することができ、Ｒ_３は、式Ｉについて定義された通りである）と反応させること、ならびにそれぞれの場合に、所望により、この方法に従って又は他の方法で得ることができるそれぞれの場合に遊離形又は塩形での式（ＩＩ）の化合物を式（ＩＩ）の他の化合物に転換し、この方法に従って得ることができる異性体の混合物を分離し、および所望の異性体を単離し及び／又はこの方法に従って得ることができる式（ＩＩ）の遊離化合物を塩に転換するか又はこの方法に従って得ることができる式（ＩＩ）の化合物の塩を式（ＩＩ）の遊離化合物若しくは他の塩に転換すること、を特徴とする方法である。

(This compound is known or can be prepared in the same manner as the corresponding known compound, wherein R ₁ , R ₄ , R ₅ , R ₆ , X and n are represented by the formula (I Can be prepared analogously to inorganic or organic cyanides and compounds of the formula R ₃ —NH ₂ , which are known or the corresponding known compounds, R ₃ is as defined for formula I) and in each case, in each case in free or salt form, which can be obtained according to this method or otherwise if desired. Is converted to other compounds of formula (II), the mixture of isomers obtainable according to this method is separated, and the desired isomer is isolated and / or obtained according to this method Can Converting a free compound of formula (II) into a salt or converting a salt of a compound of formula (II) obtainable according to this method into a free compound of formula (II) or other salts It is a method to do.

  Suitable cyanides are sodium cyanide, potassium cyanide, trimethylsilyl cyanide and acetone cyanohydrin.

  The compounds of formula (I) obtainable according to this method or by other methods are in a manner known per se, in which one or more substituents of the starting compound of formula (I) are substituted in the customary manner. Can be converted to different compounds of formula (I) by substitution with other substituents according to the invention.

  Depending on the reaction conditions and starting materials chosen as appropriate in each case, only one substituent may be replaced by another substituent according to the invention in one reaction step. It is possible or in the same reaction step, a plurality of substituents can be replaced by other substituents according to the invention.

  The salt of the compound of the formula (I) can be produced by a method known per se. For example, an acid addition salt of a compound of formula (I) is obtained by treatment with a suitable acid or a suitable ion exchange reagent, and a salt with a base is treated with a suitable base or a suitable ion exchange reagent. Can be obtained.

  Salts of compounds of formula (I) can be converted to the free compounds of formula (I) by conventional means. That is, an acid addition salt can be converted, for example, by treatment with a suitable basic medium or a suitable ion exchange reagent, and a salt with a base can be converted, for example, with a suitable acid or a suitable ion exchange reagent. It can be converted by processing.

  Salts of compounds of formula (I) can be converted into different salts of compounds of formula (I) by methods known per se. For example, a salt of an inorganic acid (such as hydrochloric acid), an appropriate metal salt of the acid (such as a sodium salt, barium salt or silver salt) (such as with silver acetate), and an inorganic salt (such as silver chloride) formed is insoluble. Thus, the acid addition salt can be converted to a different acid addition salt by treatment in a suitable solvent that precipitates from the reaction mixture.

  Depending on the method and / or reaction conditions, compounds of formula (I) having salt-forming characteristics can be obtained in free form or in the form of salts.

  Compounds of formula (I) can also be obtained in the form of their hydrates and / or any other solvent (eg any that can be used for crystallization of the compound in solid form) Solvent).

  The compounds of formulas (I) and (II) may be in the form of one of the possible isomers or in the form of mixtures thereof, for example depending on the number of asymmetric carbon atoms and their absolute and relative configurations. In the form of pure isomers such as enantiomers and / or diastereoisomers or mixtures of enantiomers, eg mixtures of isomers such as racemates, mixtures of diastereoisomers or mixtures of racemates. May exist in form. The present invention relates to both pure isomers and mixtures of all possible isomers. It is to be understood in this document that the details of the stereochemistry are not specifically stated in each case.

  Depending on the starting materials and methods selected, mixtures of diastereoisomers and racemates of the compounds of the formulas (I) and (II) obtainable according to this method or by other methods are known The method can be separated into pure diastereoisomers or racemates, for example by fractional crystallization, distillation and / or chromatography, based on the physicochemical differences between the components.

  The mixture of enantiomers or racemates obtained in this way can be chromatographed on chiral adsorbents, for example by recrystallization from optically active solvents, for example with the aid of suitable microorganisms, by known methods. By means of high performance liquid chromatography (HPLC) on acetylcellulose, by cleavage with a specific immobilized enzyme or, for example, using a chiral crown ether, in which case only one enantiomer is formed Can be separated into optical antipodes.

  Pure diastereoisomers and enantiomers are obtained not only by separation of the corresponding mixture of isomers, but also in accordance with the present invention generally known methods of diastereoselective or enantioselective synthesis, eg suitable It can be obtained by carrying out the process according to the invention with starting materials having stereochemistry.

  As long as the individual components have different biological activities, it is advantageous to isolate or synthesize isomers, such as enantiomers or mixtures of isomers, such as mixtures of enantiomers, which are more biologically active. It is.

  In the process according to the invention, the starting materials and intermediates leading to the compounds of formula (I) described at the outset as particularly valuable are preferably used.

  The invention particularly relates to the production methods described in the examples.

  The invention also relates to the novel starting materials and intermediates used according to the invention in the preparation of compounds of formula (I), their use and methods for their preparation.

  In the area of pest control, the compounds of the formula (I) according to the invention are valuable in a highly advantageous biocidal zone while being well tolerated by warm-blooded animals, fish and plants even at low concentration ratios. It is an active ingredient that exhibits preventive and / or curative activity. This compound is particularly suitable for use in areas that control animal endo and ectoparasites and plant harmful insects and representatives of ticks. The active ingredients according to the invention are effective against all or individual developmental stages of normally susceptible animal pests, but all or individual growth of resistant animal pests such as insects and representatives of the order of mites It is also effective for stages. The pest control activity of the active ingredient according to the invention can manifest itself directly, i.e. immediately or after only a short time, e.g. with the pest mortality occurring during molting. In particular, it can be manifested, for example, by a reduced egg-laying rate and / or hatching rate, with good activity corresponding to a mortality rate of at least 50-60%. The compounds of formula (I) are particularly distinguished by an unusually long duration of action.

  The animal pests of the plant include those described in EP-A-736 252, page 5, line 55 to page 6, line 55. Accordingly, the pests described therein are included in the subject matter of the present invention by reference.

  The compounds of the formula (I) are also suitable for pests affecting hygiene, in particular the fly order, butterfly order, Diptoptoptera order, including the family Sarcophagidae, Anophylidae and Clicidae. (E.g., Blattidae) and bees (e.g., Formicidae).

  The compounds of formula (I) also have long-lasting activity in the case of plant parasites, ticks and insects. In the case of ticks, they are effective against Tetranychidae (Tetranychus and Panonychus) eggs, nymphs and adults.

  These include, among others, the sucking insects, especially the Aphididae family, the Delphacidae family, the Ciccadellidae family, the Psyllidae family, the Loccidae family, the Loccidae family, and the Loccidae family. (Diaspididae) and Eriophydidae (e.g., rust mites on citrus fruits); Hemioptera, Heteroptera and Thyanotera p Coleoptera, Flyptera (Diptera) and Grasshopper (Orth) It has a high activity at the herbivorous insects ptera).

  They are also suitable as soil insecticides against pests in the soil.

  The compounds according to the invention are particularly suitable on plants, and more particularly on plants and ornamental plants useful in agriculture, horticulture and afforestation or such as fruits, flowers, leaves, stems, tubers or roots. Exterminate, i.e. suppress or eradicate the above-mentioned types of pests that develop on some plant parts, in some cases later plant parts that still protect against these pests Can be used for.

  Thus, the compound of formula (I) comprises cereals (eg wheat, barley, rye, oats, rice, corn and sorghum); beets (eg sugar beet and feed beet); fruits (eg apples, pears, plums). Peaches, almonds, cherries, berries (such as strawberries, raspberries and blackberries) pears, drupes and berries); leguminous plants (such as broad beans, lentils, peas and soybeans); Oily plants (such as poppies, olives, sunflowers, coconuts, castors, cacao and peanuts); cucurbits (such as pumpkins, cucumbers and melons); fiber plants (such as cotton, flax, Asa and jute); Citrus fruits (such as orange, lemon, grapefruit and mandarin); Vegetables (such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes and paprika); camphoraceae (such as avocados, cinnamon and camphor); and tobacco, nuts, coffee, eggplant, sugar cane, tea, It is effective for all growth stages of fluke and herbivorous insects on crops such as pepper, grapes, hops, bananas, natural rubber plants and ornamental plants.

  Compounds of formula (I) may also include Meloidogyne species, Heterodera species, Pratylenchus species, Ditylenchus species, Radophorus species, Rhizoglis species Effective against plant nematodes.

  In the context of the present invention, ectoparasites occurring as parasites on warm-blooded organisms are understood to mean in particular insects, ticks and ticks, which include Lepidoptera, Coleoptera , Homooptera, Heteroptera, Flies (Diptera), Thrips (Thysanoptera), Grasshoppers (Oroptoptera), Lice (Anoplura), Fleas (Siphonaptera), M , Insects of the order Thysanura, Isoptera, Psocoptera and Hymenoptera. However, ectoparasites that can be mentioned in particular are those that bother humans or animals and carry pathogens, such as the housefly (Musca domestica), Musca vetustissima, Musca autumalis, the princess housefly (Fan canicularis), Sarukofaga-Karunaria (Sarcophaga carnaria), sheep Kinbae (Lucilia cuprina), cow skin fly (Hypoderma bovis), Hipoderuma-Rineatsumu (Hypoderma lineatum), Kurisomia-Kuroropiga (Chrysomyia chloropyga), South America bot (Dematobia hominis), Cocryomia Ho Niborax (Cochliomyia hominivorax), Gasterophilus intestinalis, Oestrus ovis, Estrus calcium (Stomoxys calcitrans) Chironomidae (L. elegans) such as Simuliidae, Psychodidae, and blood-sucking parasites, such as Ctenocephalides felis and Ctenocephalides canis (Cats and Dogs) Xenopsyl fleas such as a cheopis, human fleas (Pulex irritans), fleas such as Dermatophilus penetran, lice such as Damarina ovnis, pediculian humanis, abalone flies and abalone flies Haematopota species such as Haematopota pluvialis, Tabinidae species such as Tabanas nigrovittus, Tabisidae cs. tsetse flies such as Lossinia species, biting insects, especially cockroaches such as Bratella germanica, Blatta orientalis, Periplaneta americana (Sarcoptes scabiels), ticks such as sheep Soroptes and Psorergates species and especially ticks. The latter belongs to the order Acarina. Known examples of ticks include, for example, Boophilus, Amblyomma, Anocentor, Dermacentor, Haemaphysalis, Hyalema I, and Tick Ix , Rhipicentor, Margaropus, Rhipicephalus, Argas, Otobius, Ornithodoros, etc., these are cattle, Breeding for farm animals such as sheep, goats, poultry such as chickens, turkeys and geese, fur such as minks, foxes, chinchillas, rabbits etc. It is to have not only livestock, such as animals and cats and dogs, flock prefer to warm-blooded animals, including man.

  In addition, the compounds of formula (I) can be used for the serious diseases of endoparasite nematodes and flukes in mammals and poultry such as sheep, pigs, goats, cattle, horses, donkeys, dogs, cats, guinea pigs and ornamental birds. It is especially effective against worms that can cause it. Typical nematodes in this condition are: Hemoncas, Ciliate nematode, Ostertasia, Nematodilus, Couperia, Ascaris, Bunostumum, Oesophagogostnum, Charbertia, Trichris, Enchu, Enchu Trichonema, Dictirocaurus, Capilaria, Heterakis, Toxocara, Ascaridia, Oxyuris, Ancylostoma, Uncinaria, Inca kaichu, and Inukaichu. Among the flukes, mention must be made in particular of the family Fascioliideae, in particular Fasciola hepatica. A particular advantage of the compounds of formula (I) is their efficacy against nematodes that are resistant to benzimidazole-based active ingredients.

  Certain Nematodirus, Coopeia and Oesophagostonum attack the host animal intestinal tract, while Haemonchus and Ostertagia species Parasitize in the stomach, and those of the Dictyocaurus species parasitize in lung tissue. Parasites of the family Filariidae and Setariidae are found in internal cellular tissues and organs such as the heart, blood vessels, lymphatic vessels and subcutaneous tissue. In this context, the dog canine filamentous, Dirofilaria immitis, must be mentioned. The compounds of formula (I) are very effective against these parasites.

  Furthermore, the compounds of formula (I) are suitable for combating parasites that are human pathogens. Among these, typical representatives appearing in the gastrointestinal tract include: Ancylostoma species, Necator species, Ascaris species, Strongyloides species, Trichinella species, Capillaria ) Species, Trichuris species and Enterobius species. The compounds of the present invention are also present in the blood, tissues and in various organs, from the species of the family Filiaridae, Wuchereria species, Brugia species, Onchocerca species and Loir filamentous species. It is effective against worm species and also against parasites of Dracunculus and Strangleroides and Trichinella species, which in particular affect the gastrointestinal tract.

  In the field of crop protection, the compounds of formula (I) are used in unmodified form or preferably with additives commonly used in the compounding art. Thus, it can be formulated in known manner, for example into emulsifiable concentrates, direct dilutable solutions, dilute emulsions, soluble powders, granules and encapsulates in polymeric substances. Depending on the properties of the composition, the method of application is selected according to the intended purpose and general circumstances.

  The invention also includes emulsifiable concentrates, suspension concentrates, direct sprayable or dilutable solutions, coating pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules Or a pest control agent, such as an encapsulated product in a polymer material, which contains at least one active ingredient of the present invention and the type of formulation is selected according to the intended purpose and general circumstances About. These are prepared in a known manner, for example by intimately mixing and / or grinding the active ingredient together with extenders such as solvents, solid carriers and optionally surface-active compounds (surfactants).

  The active ingredient is in pure form in these compositions, i.e. solid active ingredient, e.g. in a specific particle size, or preferably like a bulking agent, e.g. solvent or solid carrier or surface active compound (surfactant). It is used with at least one additive commonly used in the compounding art.

  As compounding additives, for example, solid carriers, solvents, stabilizers, “delayed release” additives, dyes and optionally surface active substances (surfactants) are used. Suitable carriers and additives include any material commonly used in crop protection products, particularly snail and slug control products. Suitable additives such as solvents, solid carriers, surface active compounds, nonionic surfactants, cationic surfactants, anionic surfactants and other additives in the compositions used according to the present invention Examples include those described in European Patent Application Publication No. EP-A-736 252, page 7, line 51 to page 8, line 39. These are included in the subject matter of the present invention by reference.

  Compositions for use in crop protection are generally 0.1 to 99% by weight, in particular 0.1 to 95% by weight of active ingredient and 1 to 99.9% by weight, in particular 5 to 99.9. % By weight of at least one solid or liquid additive is included, and generally 0 to 25%, in particular 0.1 to 20% by weight of the composition can constitute the surfactant. Commercial products are preferably formulated as concentrates, but end users typically use dilute formulations with lower active ingredient concentrations. Preferred compositions used in crop protection have in particular the following composition (% =% by weight):

Emulsifiable concentrate:
Active ingredient: 1 to 95%, preferably 5 to 20%
Surfactant: 1-30%, preferably 10-20%
Solvent: 5-98%, preferably 70-85%
dust:
Active ingredient: 0.1 to 10%, preferably 0.1 to 1%
Solid carrier: 99.9-90%, preferably 99.9-99%
Suspension concentrate:
Active ingredient: 5-75%, preferably 10-50%
Water: 94-24%, preferably 88-30%
Surfactant: 1-40%, preferably 2-30%
Wet powder:
Active ingredient: 0.5-90%, preferably 1-80%
Surfactant: 0.5-20%, preferably 1-15%
Solid carrier: 5 to 99%, preferably 15 to 98%
Granules:
Active ingredient: 0.5-30%, preferably 3-15%
Solid carrier: 99.5-70%, preferably 97-85%

  A roundworm control composition according to the invention for controlling animal parasites in and on warm-blooded organisms comprises 0.1 to 99% by weight, in particular 0.1 to 95% by weight of the formula (I) Compounds and solid or liquid auxiliaries containing 99.9 to 1% by weight, in particular 99.8 to 5% by weight, 0 to 25% by weight, in particular 0.1 to 25% by weight, of surfactants. .

  Preferred forms of administration for use in warm-blooded animals to combat worms include solutions, emulsions, suspensions (drench), food additives, powders, tablets including boiling tablets, large pills ( boli), capsules, microcapsules and pour-on formulations. It must be ensured that the formulation additive is physiologically acceptable.

  Suitable solvents in the use of the formulations for controlling animal parasites are, for example, alcohols such as ethanol, propanol or butanol, glycols, and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene Glycols, ethylene glycol monomethyl ether or monoethyl ether, ketones such as cyclohexanone, isophorone or diacetone alcohol, strong solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide or water, vegetable oils such as rapeseed oil, Castor oil, coconut oil or soybean oil and silicone oil if appropriate.

  Suitable binders for tablets and large pills are chemically modified natural polymeric substances that are soluble in water or alcohol, such as starch, cellulose or protein derivatives (eg methylcellulose, carboxymethylcellulose, ethylhydroxyethylcellulose). And proteins such as zein and gelatin) and synthetic polymers such as polyvinyl alcohol and polyvinyl pyrrolidone. Tablets also contain fillers (eg, starch, microcrystalline cellulose, sugar, lactose, etc.), lubricants and disintegrants.

  When the anthelmintic composition is in the form of a feed concentrate, for example, a high-performance feed, feed grain or protein concentrate is used as a carrier. Such feed concentrates or compositions also include, besides active ingredients, supplements, vitamins, antibiotics, chemotherapeutic agents or other pest control agents, in particular bacteriostatic agents, fungistatic agents, anticoccidial agents And hormonal preparations, substances having an anabolic effect or substances that promote growth, substances that affect the quality of meat of a disassembled animal, or substances that are otherwise beneficial to the organism. When the composition or compound of formula (I) contained therein is added directly to the feed or beverage trough, the final feed or beverage trough is preferably about 0.0005 to 0.02 wt. The active ingredient is contained at a concentration of 5% (5 to 200 ppm).

  The compounds of formula (I) according to the invention can be used alone or in combination with other biocides. For example, to increase the effect, they can be combined with a pest control agent having the same direction of action, or in order to expand the zone of activity, they are combined with substances having different directions of action. Can do. It is also advantageous to add so-called “repellents”. If it is desired to extend the range of activity to endoparasites, such as helminths, the compounds of formula (I) are advantageously combined with substances having endoparasitic properties. Of course, they can also be used in combination with antibacterial agents. Since the compounds of formula (I) are “nematicides”, ie they are particularly effective against the adult stage of the target parasite, they are more effective against the larval stage of the parasite. It is very advantageous to add This is because, in this way, the main part of these parasites that cause large-scale economic damage will be captured and will contribute more significantly to avoiding the formation of resistance. Some combinations also lead to a synergistic effect. That is, the total amount of active substance used can be reduced, which is desirable from an ecological point of view. Preferred groups of combination partners and particularly preferred combination partners are listed below, and the combination may contain one or more of such partners in addition to the compound of formula (I).

  Suitable mixing partners for use in crop protection and for use in combating endo- and ectoparasites on warm-blooded organisms are biocides such as the insecticides and acaricides listed below. Yes, well known to those skilled in the art, these have different mechanisms of action, eg, chitin synthesis inhibitors, growth regulators; active ingredients that act in the same manner as larval hormones; act as insecticides Active ingredients; broadband insecticides, broadband acaricides and nematicides; and well-known anthelmintic and insect-and / or mite repelling agents, repellents and separating agents.

Examples of suitable insecticides and acaricides are azamethiphos, chlorfenvinphos, cypermethrin, cypermethrin hysis, cyromazine, diafenthurone Diazinon, dichlorvos, dicrotophos, dicyclanil, phenoxycarb, phenoxycarb, fozuron, fosiofen, thiophene , Le From fenfenlon, methacrifos, methidathion, monocrotophos, phosphamidon, profenofos, diphenenlan, diphenenlan, dienenlan Substances obtainable from NCTC 11821, pymetrozine, bromopropyrate, methoprene, disulfuton, quinalphos, τ-fulvalinate (tau-fluva) inate, thiocyclam, thiomethon, aldicarb, azinephos-methyl, benfurcarb, bifenthrin, buprofen (b), buprofen (b), buprofen (b) dibutyraminothio, cartap, chlorfluazuron, chlorpyrifos, cyfluthrin, λ-cyhalothrin, α-cyhalothrin, α-cyhalothrin Cypermethrin, deltamethrin, diflubenzuron, endosulfan, etiofencarb, fethiothion, fenocarb, fenocarb, fenocarb, fenocarb. Heptenophos, imidacloprid, isoprocarb, methamidophos, methomyl, mevinphos, parathion on), parathion-methyl, fosalone, pirimicarb, propoxur, teflubenzuron, terbufos, triazamate, f, tenobuf -Cyfluthrin, silafluofen, fenpyroximate, pyridaben, phenazaquin, pyriproxyfen, pyrimidendram. Purido (acetamiprid), avermectin _{B 1 (avermectin B} 1) (abamectin (abamectin)), emamectin (emamectin), Emamectin benzoate, spinosad (spinosad), plant extracts that are active against insects, activity against insects A nematode-containing preparation, a preparation obtainable from Bacillus subtilis, a preparation containing a fungus active against insects, a preparation containing a virus active against insects, chlorfenapyr (Chlorfenapyr), acephate, acrinathrin, alanicarb, alphamethrin , Amitraz, Az60541, Azinphos A, Azinphos M, Azocyclotin, Bendiocarb, Bensultap, β-CyflutM, Beta-Cyflux , Bromophos A, bufencarb, butocaboxin, butylpyridaben, cadusafos, carbaryl, carbophenothion, carbophenothion, carbophenothion, carbophenothion, carbophenothion. Ethoxyphos (chlorethoxyfos), chlormefos (chlormephos), cis-resmethrin (cis-resmethrin), crocitrin, clofenthezine, cyanophos (cyanophos), cycloprotothine (cycloprothine) M (demethon M), demeton S, demeton-S-methyl, diclofenthion, diclifos, diethion, dimethoate, dimethylvinphos, dioxathion, dioxathion, dioxathion Edifenphos, esfenvalerate, ethion, etofenprox, ethoprophos, etrimphos, fenamiphos, fenbutatin oxide (fenbutin oxide) fenothiocarb, fenpropatrin, fenpyrad, fenthion, fluazinam, flucycloxuron, flucytriton flutonrinox ), Flufenprox, fonophos, fothiazate, fubufenprox, HCH, hexaflumuron, hexythiazos, pI-220 (Isofenphos), isoxathion (ioxathion), ivermectin (vermectin), malathion (malathion), mecarbam, mesulfenphos (metalsulfide), metaldehydride (metholcarbine) Moxidectin, nared, NC184, ometoate, oxamyl, oxydemethon M, oxydeprofos, permethrin, phenate, phenate ), Phosmet, phoxim, pirimiphos M, pirimiphos E, promecarb, propopafos, prothiofos, proto-ato, pyrophos Fenthion (pyrada-p henthion, pyrethmethrin, pyrethrum, tebufenozide, salithion, cebufos, sulfotep, sulprophos (sultep) tefluthrin, temephos, terbam, tetrachlorvinphos, thiacloprid, thiafenox, thiamethoxam, thiodicalb carb, thiophanox, thionazin, thuringiensin, tralomethrin, triarthene, triazophos, triazolone, triazolone, triazolone, triazolone (Trimethacarb), bamidithione (xylylcarb), YI5301 / 5302, zetamethrin, DPX-MP062-indoxacarb, methoxyphenozide (methoxyphene) Zide), Bifenazato (bifenazate), an XMC (3,5-xylyl methylcarbamate) or fungal pathogen Metarhizium anisopliae. The listed mixing partners are very well known to those skilled in the art. Most are described in various editions of the Pesticide Manual, The British Crop Protection Council, London, while others are in the Merck Index (The It is described in various editions or patent literature of Merck Index, Merck & Co., Inc., Rahway, NJ, USA.

  Examples of suitable anthelmintic agents that can be added to the composition are described below. Many of these examples have insecticidal and acaricidal activity in addition to anthelmintic activity, some of which have already been listed above.

(A1) praziquantel = 2-cyclohexylcarbonyl-4-oxo-1,2,3,6,7,11b-hexahydro-4H-pyrazino [2,1-α] isoquinoline (A2) closantel = 3,5-diiodo-N- [5-chloro-2-methyl-4- (a-cyano-4-chlorobenzyl) phenyl] salicylamide (A3) triclabendazole = 5-chloro-6- ( 2,3-dichlorophenoxy) -2-methylthio-1H-benzimidazole (A4) levamisol = L-(−)-2,3,5,6-tetrahydro-6-phenylimidazole [2,1b] thiazole (A5) Mebendazole = 5-Benzoyl-1H-benzimidazol-2-yl) carbamic acid methyl ester (A6) Omphalotin = the fungus Omphalotus olearius described in WO 97/20857 Macrocyclic fermentation product (A7) Abamectin = Avermectin B1
(A8) Ivermectin = 22,23-dihydroavermectin B1
(A9) Moxidectin = 5-O-demethyl-28-deoxy-25- (1,3-dimethyl-1-butenyl) -6,28-epoxy-23- (methoxyimino) -milbemycin B
(A10) Doramectin = 25-cyclohexyl-5-O-demethyl-25-de (1-methylpropyl) -avermectin A1a
(A11) Milbemectin = Milbemycin A3 and Milbemycin A4 mixture (A12) Milbemycin oxime = Milbemectin 5-oxime

Examples of suitable repellent materials (repellents and separating agents) are, for example:
(R1) DEET (N, N-diethyl-m-toluamide)
(R2) KBR3023 N-butyl-2-oxycarbonyl- (2-hydroxy) -piperidine (R3) cymazol = N, -2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene -2,4-Xylidine.

  In view of the above, a further substantial aspect of the present invention is a combination formulation for the control of parasites in warm-blooded organisms, in addition to the compound of formula (I) , A combination preparation comprising at least one other active ingredient having the same or different direction of action and at least one physiologically acceptable carrier. The present invention is not limited to two-component combinations.

  The composition according to the invention can be administered to the animal being treated by topical, oral, parenteral or subcutaneous means, the composition comprising a solution, emulsion, suspension ( Drench), powders, tablets, large pills, capsules and pour-on formulations.

  For pore-on or spot-on methods, the compound of formula (I) is applied to a specific location on the skin or fur of the animal, preferably behind the animal's neck or spine Is included. This is done, for example, by applying a swab or spray of a pour-on formulation or a spot-on formulation to a relatively small area of the fur from which the active ingredient is assisted by animal movement. By the action of the developing components of the blend, it is almost automatically distributed over a large area of the fur.

Pore-on and spot-on formulations advantageously promote a rapid dispersion on the surface of the host animal's skin or in the fur and have a carrier commonly referred to as a developing oil. Contained. For example, oily solutions; alcoholic and isopropanolic solutions such as solutions of 2-octyldodecanol or oleyl alcohol; isopropyl myristate, isopropyl palmitate, lauric oxalic ester, oleic oleic ester, oleic acid decyl ester, hexyl laurate, oleyl oleate, solutions of esters of dicarboxylic acids such as oleic acid decyl, capric acid esters of saturated fatty alcohols of chain length C ₁₂ -C _18; dibutyl phthalate, isophthalate Suitable are solutions of esters of dicarboxylic acids such as diisopropyl, diisopropyl adipic acid, di-n-butyl adipate or esters of aliphatic acids, for example glycols. Advantageously, a dispersant known from the drug or cosmetic industry is also present. Examples are 2-pyrrolidone, 2- (N-alkyl) pyrrolidone, acetone, polyethylene glycol and its ethers and esters, propylene glycol or synthetic triglycerides.

  Oily solutions include, for example, vegetable oils such as olive oil, peanut oil, sesame oil, pine oil, linseed oil or castor oil. The vegetable oil may also be present in epoxidized form. It is also possible to use paraffin and silicone oil.

  Generally, a pour-on formulation or a spot-on formulation contains 1 to 20% by weight of a compound of formula (I), 0.1 to 50% by weight of a dispersant and 45 to 98.9% by weight of a solvent. Contained.

  The pore-on method or spot-on method is especially useful for herds such as cows, horses, sheep or pigs where it is difficult or time consuming to treat all animals orally or by injection. It can be used advantageously. Because of its simplicity, this method can of course be used for all other animals, including individual livestock or pets, and it is often performed without veterinary professional assistance. It is highly preferred by animal growers because it can.

  Commercial products are preferably formulated as concentrates, but end users usually use dilute formulations.

  Such compositions also contain other ingredients such as stabilizers, antifoams, viscosity modifiers, binders or tackifiers, as well as other active ingredients for obtaining special effects. Good.

  The present invention also relates to such an anthelmintic composition for use by end users.

  In each of the methods according to the invention for combating pests, or in each of the pest control compositions according to the invention, the active ingredient of formula (I) may be in any spatial configuration or Mixtures can also be used.

  The present invention also provides a method for the prophylactic protection of warm-blooded organisms, in particular productive livestock, livestock and pets against parasitic helminths, comprising the active ingredient of formula (I) or Included is a method comprising dosing the manufactured active ingredient formulation as an additive to a feed or beverage trough or in solid or liquid form, orally, by injection or parenterally. The present invention also includes a compound of formula (I) according to the present invention for use in one of the aforementioned methods.

  The following examples are merely intended to illustrate the present invention without limiting it. The expression “active ingredient” indicates one of the substances listed in the table.

A preferred formulation for use in combating parasites on warm-blooded organisms has the following composition: (% = Weight percent)
1. Granules a) b)
Active ingredient from Table 1 or 2 5% 10%
Kaolin 94% −
Highly dispersible silicic acid 1% −
Attapulgite-90%
The active ingredient is dissolved in methylene chloride and sprayed onto the carrier, then the solvent is evaporated off in vacuo. Such granules can be mixed into animal feed.

2. Granules Active ingredient 3% from Table 1 or 2
Polyethylene glycol (MW200) 3%
Kaolin 94%
(MW = molecular weight)
The finely ground active ingredient is uniformly applied to kaolin moistened with polyethylene glycol in a mixer. In this way, dust-free coated granules are obtained.

3. Tablets and large pills I Active ingredient from Table 1 or 2 33.00%
Methylcellulose 0.80%
Highly dispersed silicic acid 0.80%
Corn starch 8.40%
II Crystalline lactose 22.50%
Corn starch 17.00%
Microcrystalline cellulose 16.50%
Magnesium stearate 1.00%

  I Stir methylcellulose into water. After the material swells, the silicic acid is stirred in to suspend the mixture uniformly. Mix active ingredient and corn starch. This aqueous suspension is contained in the resulting mixture and kneaded to a dough. The resulting mass is granulated through a 12M sieve and dried.

  II Thoroughly mix all four excipients.

  III Mix the premix obtained according to I and II and compress into tablets or large pills.

4). Injectable formulation Oily vehicle (slow release)
1. Active ingredient 0.1 to 1.0 g from Table 1 or 2
Add peanut oil to 100 mL. Active ingredient 0.1 to 1.0 g from Table 1 or 2
Sesame oil added to 100 mL Formulation: Active ingredient is stirred and optionally slowly heated to dissolve in a portion of the oil, and after cooling, the solution is brought to the desired volume and the appropriate 0.22 micron Sterile filter through a membrane filter.

B. Water miscible solvent (medium release rate)
Active ingredient 0.1 to 1.0 g from Table 1 or 2
4-hydroxymethyl-1,3-dioxolane
(Glycerol formal) 40g
Add 1,2-propanediol to 100 mL Active ingredient from Table 1 0.1-1.0 g
Glycerol dimethyl ketal 40g
1,2-propanediol added to 100 mL Formulation: The active ingredient is dissolved in a portion of the solvent with stirring, the solution is brought to the desired volume and sterilized through an appropriate 0.22 micron membrane filter. Filter.

C. Aqueous lysate (fast release)
1. Active ingredient 0.1 to 1.0 g from Table 1 or 2
10g polyethoxylated castor oil (40 ethylene oxide units)
1,2-propanediol 20g
Benzyl alcohol 1g
Water addition injection Add to 100 mL Active ingredient 0.1 to 1.0 g from Table 1 or 2
Polyethoxylated sorbitan monooleate (20 ethylene oxide units) 8g
4-hydroxymethyl-1,3-dioxolane
(Glycerol formal) 20g
Benzyl alcohol 1g
Water Addition Injection Add to 100 mL Formulation: Active ingredient is dissolved in solvent and surfactant and the solution is made up to the desired volume with water. Sterile filtration is then performed through a suitable membrane filter having a pore diameter of 0.22 microns.

5). Pore-on type
Active ingredient 5g from Table 1 or 2
10g isopropyl myristate
Add isopropanol to 100 mL.
Active ingredient 2g from Table 1 or 2
Hexyl laurate 5g
Medium chain length triglyceride 15g
Add ethanol to 100 mL C.I.
Active ingredient 2g from Table 1 or 2
Oleic oleate 5g
N-methylpyrrolidone 40g
Isopropanol added to 100 mL This aqueous system can preferably be used for oral and / or intragastric application.

  The composition also includes stabilizers such as vegetable oils and epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soybean oil), antifoaming agents such as silicone oils, preservatives, viscosity modifiers, binders Other ingredients such as agents, tackifiers and fertilizers and other active ingredients for obtaining special effects may be included.

  Another biologically active substance or additive as well as mineral salts or vitamins that have a neutral behavior with respect to the compound of formula (I) and that do not have a detrimental effect on the host animal to be treated are added to the above composition. It is also possible to add.

  The composition according to the invention, in a known manner, in the absence of additives, for example, crushing, sieving and / or compressing a solid active ingredient or a mixture of active ingredients, eg to a specific particle size. Or in the presence of at least one additive by intimately mixing and / or grinding the active ingredient or a mixture of active ingredient and additive (s). The invention also relates to a process for the production of the compositions according to the invention and the use of the compounds of formula (I) in the production of these compositions.

  The present invention also provides a method for applying this composition, i.e. spraying, atomizing, spreading, coating, dressing, scattering or infusion, selected according to the intended purpose and prevalence. The present invention relates to a method for controlling types of pests and to the use of a composition for controlling the types of pests. A typical concentration ratio is 0.1 to 1000 ppm, preferably 0.1 to 500 ppm of active ingredient. The application rate per hectare is generally 1 to 2000 g, in particular 10 to 1000 g / ha, preferably 20 to 600 g / ha, of active ingredient per hectare.

  The preferred application method in the field of crop protection is the application to the leaves of plants (foliar application), the number of applications and the application ratio depending on the risk of flocking by the pests in question. However, the active ingredient can also be used if the liquid formulation soaks into the plant site or if the active ingredient is included in the plant site, for example in the soil, in solid form, for example in granular form (soil application). ), Can penetrate the plant through the roots (osmotic action). In paddy rice crops, such granules can be applied in a metered amount to padded rice fields.

  The composition according to the invention can also be used to protect plant propagation material, including genetically modified propagation material, for example seed material or fruit cuttings including fruits, tubers or grains, from animal pests. Is also suitable. The propagation material can be treated with the formulation prior to planting, for example, the seed can be dressed before sowing. The compounds according to the invention can also be applied to the grain by impregnating the grain with a liquid formulation or coating the grain with a solid formulation (coating). The formulation can also be applied to the planting site when planting the propagation material, for example, between seedlings. The present invention also relates to a method for treating plant propagation material and the plant propagation material thus treated.

  The following examples serve to illustrate the invention. These do not limit the invention. The symbol “h” represents “time”.

(Production Example)
Preparation of N- (1-cyano-1- [2,3-dichlorophenoxymethyl] ethyl) -C-phenylmethanesulfonamide a) 5 g 2,3-dichlorophenol, 4 g 2-chloroacetone, 4.7 g A mixture of anhydrous potassium carbonate and 450 mg potassium iodide is refluxed in 50 mL acetone for 6 hours, then cooled to room temperature and filtered. The filtrate is evaporated. In this way, 1- (2,3-dichlorophenoxy) acetone is obtained.

  b) 6.5 g of 1- (2,3-dichlorophenoxy) acetone, 1.76 g of sodium cyanide and 2.4 g of ammonium chloride are added to 30 mL of 25% ammonia solution and the mixture is allowed to come to room temperature. Stir for 24 hours. The crude product is then extracted from the mixture using ethyl acetate, the organic phase is separated off, washed with water and saturated sodium chloride solution, dried using magnesium sulphate and evaporated. In this way, 2-amino-3- (2,3-dichlorophenoxy) -2-methylpropionitrile is obtained.

  c) 5.2 g of α-toluenesulfonyl chloride was added 6.6 g 2-amino-3- (2,3-dichlorophenoxy) -2-methylpropionitrile and 4.86 g in 50 mL methylene chloride. Add to the mixture of ethyldiisopropylamine and stir the mixture at room temperature for 24 hours. The crude product is then extracted from this mixture with ethyl acetate and the organic phase is separated, washed with aqueous sodium bicarbonate solution and saturated sodium chloride solution, dried using magnesium sulphate and evaporated. The residue is purified by high pressure column chromatography on silica gel using hexane / ethyl acetate (2: 1). In this way the title compound is obtained.

  The substances listed in the table below can also be produced in the same manner as described above. Melting point values are given in ° C.

(Biological Example)
A. Exterminating animal parasites (Example B.1)
In vivo study on orally-administered gerbils (Meriones unguiculatus) against Colbriformis ciliate nematodes (Trichostrongylus colbriformis) and torsion-like nematodes (Haemonchus contortus) 6 to 8 weeks old gerbils Infected by artificial feeding containing approximately 2000 third instar larvae of each of the missed and torsional ciliate nematodes. 6 days after infection, were lightly anesthetized with _{N 2} O in gerbils, by using the amounts of 100,32 and 10-0.1mg / kg, mixture of 2 parts DMSO and 1 part polyethylene glycol (PEG300) Treatment is by oral dosing with a test compound dissolved in it. On the 9th day (3 days after treatment), most of the 4th instar torsion-like nematode larvae and most of the Colbriformis ciliate nematodes are immature adults, and gerbils were used to count worms. kill. Efficacy is calculated as the% reduction in the number of worms in each gerbil by comparing to the geometric mean of the number of worms in 8 infected and untreated gerbils.

  In this test, a strong reduction in nematode attack is achieved with the compounds of formula (I).

B. Exterminating plant pests (Example B.2)
Effect on Heliotis virescens caterpillars Young soy plants are sprayed with an aqueous emulsion spray mixture containing 400 ppm active ingredient, and after the spray coating has dried, 10 first-aged Heliotis virescens caterpillars are Let them live, then place them in a plastic container. Evaluation is performed after 6 days. The number of caterpillars and the percent decrease in eaten damage (% activity) is determined by comparing the number of dead caterpillars in the treated plants and the eaten damage to those in the untreated plants.

  The compounds in the table show good activity against Heliotis virescens in this test.

(Example B.3)
Action against Plutella xylostella caterpillars Young cabbage plants are sprayed with an aqueous emulsion spray mixture containing 400 ppm active ingredient, and after the spray coating has dried, 10 third-aged Plutella xylostella caterpillars are Let them live, then place them in a plastic container. Evaluation is carried out after 3 days. The number of caterpillars and the percent decrease in eaten damage (% activity) is determined by comparing the number of dead caterpillars in the treated plants and the eaten damage to those in the untreated plants.

  The compounds in the table show good activity against Plutella xylostella in this test.

(Example B.4)
Action on Diabrotica balteata larvae Corn seedlings are sprayed with an aqueous emulsion spray mixture containing 400 ppm of active ingredient, and after the spray coating has dried, 10 second-aged diabrotica balteata larvae lived. And then place in a plastic container. Evaluation is performed after 6 days. The percent reduction (% activity) in the number of larvae is determined by comparing the number of dead larvae in the treated plants with that in the untreated plants.

  The compounds in the table show good activity against diabrotica balta in this test.

Claims (4)

Formula for parasite control in non-human environment:

Wherein R ₁ is phenyl that is unsubstituted or substituted with one or two identical or different substituents selected from the group consisting of halogen and halo-C ₁ -C ₂ alkyl;
R ₂ is C ₁ -C ₄ alkyl; benzyl; a group consisting of halogen, nitro, C ₁ -C ₂ alkyl, halo-C ₁ -C ₂ alkyl, C ₁ -C ₂ alkoxy and halo-C ₁ -C ₂ alkoxy A phenyl substituted by 1 to 3 substituents selected from; or naphthyl], or, where appropriate, their E / Z isomers, each in the free or salt form , Use of mixtures of E / Z isomers and / or tautomers.   Method for controlling parasites, characterized in that an effective amount of at least one compound of formula (I) according to claim 1 is used against parasites in a non-human environment.   Use of a compound of formula (I) according to claim 1 in a method for controlling parasites in non-human warm-blooded animals.   Use of a compound of formula (I) according to claim 1 for the manufacture of a pharmaceutical composition against parasites in warm-blooded animals.